United States Patent 19 11 3,982,028 Bellingham (45) Sept. 21, 1976 (54) PRESERVATIVES FOR FORAGE, HAY, 3,806,600 4/1974 Lapore................................ 424/317 GRAN AND ANIMAL FEEDS FOREIGN PATENTS OR APPLICATIONS 75) Inventor: Francis Bellingham, 1,276,677 6/1972 United Kingdom....................... 99/8 Stockton-on-Tees, England OTHER PUBLICATIONS (73) Assignee: Imperial Chemical Industries Condensed Chemical Dictionary - Hawley, 8th Ed., Limited, London, England Van Nostrand, May 1971, p. 481. 22 Filed: Sept. 13, 1973 Technical News Letter, Ministry of Agriculture, 1 1/68, 10/4/68. 21 Appl. No.: 396,666 H. D. Young, Chem. Abs., v.24, 1930, p. 3595. (30) Foreign Application Priority Data Primary Examiner-Norman Yudkoff Sept. 4, 1972 United Kingdom............... 2002 Attorney,Assistant ExaminerAgent, or Firm-Cushman,Hiram H. Bernstein Darby & 52 U.S. Cl................................... 426/69; 424/317; Cushman 426/807; 426/335; 426/532; 426/636; 426/635 57 ABSTRACT (51 Int. Cl.'............................................ A23K 1100 Feedstuffs and silage for ruminants contain mixtures 58) Field of Search ........... 426/15, 227, 310, 221, of isobutyraldehyde (IBD) with mineral or fatty acids, 426/331, 335, 210, 69,807, 635, 636,532; formalin, trioxane, or urea plus chlorine, derivatives of 424/317; 252/.407; 260/526 IBD selected from isobutanol (alone or in admixture with isobutyric acid or salts thereof), isobutyl halides 56 References Cited or esters of fatty acids, isobutyrates, di-isobutyrates, UNITED STATES PATENTS and chlorinated isobutylidene diurea. 3,642,488 2/1972 Watchorn............................. 426/69 7 Claims, No Drawings 3,982,028 2 Table 1-continued PRESERVATIVES FOR FORAGE, HAY, GRAIN Additives which showed preservative properties in AND ANIMAL FEEDS compound animal feeds 5 Treatment The present invention relates to substances suitable Additive level 7 ww for feeding to animals (particularly to ruminants) in 4 IBDisobutyric acid mixtures (e.g. 3:1 to i:3) viv 2 admixture with other feedstuffs, for example in com 5 IBD facetic acid (conc.) mixtures pound feeds, feed blocks, liquid feed supplements, (c.g. 3:1 viv) 2 drenches, slow-release pellets, or the like. The sub 6 sobutanol 2 O stances may each fulfil one or more useful functions; *AGS - a mixture of adipic, glutarie and succinic acids, a by-product in the manu for example, they may act as methane inhibitors, they facture of nylon. may control rumen fermentation (which, in turn, leads to enhanced animal performance), they may act as sources of energy, they may act as preservatives for Table 2 animal feedstuffs (e.g. compound feedstuffs containing 5 Compound animal feed composition molasses, and ensiled products such as green fodder, Barley 2000g hay, grain). Wheat 1500g Wheat-feet 480g In our co-pending British patent application No: . Groundnut 308g 31045/72 filed July 3, 1972, (corresponding to U.S. Moasses 337g application Ser. No. 373,783) we have described the 20 Salt 40g Limestone 18g use of isobutyric acid (IBA) or salts or esters thereof, Dicalcium phosphate 70g either alone or in admixture with other substances, e.g. Barley - vitamin premix 250g formalin and/or sulphuric acid, as preservatives for 5000g stored products, such as compound animal feeds con taining molasses, green fodder, hay, grain. 25 Encouraged by these results, we examined isobutyr Additives were incorporated into the above composi aldehyde (IBD), which is a very cheap material, to see tion, using molasses as carrier, and the treated concen whether it, or easily-prepared derivatives thereof, ei trate was incubated at 25°C under conditions where ther alone or in combination with each other or with temperature changes could be accurately monitored. In other compounds, would be useful as a preservative, as 30 this way, microbial activity was detected by observa a methane-inhibitor, as an agent for controlling (reduc tions of rapid temperature rises during the first six ing or stimulating) rumen fermentation, and/or as a weeks of storage. In addition, chemical and microbio source of energy. It was hoped that at least one such logical analyses were carried out to assess the extent of compound or mixture would be useful for at least one deterioration which might have occured during stor such purpose, and this proved to be the case. 35 age. The present invention accordingly provides animal Table 3 feedstuffs, in particular compound feeds, feedblocks, liquid feed supplements, drenches, slow release pellets Temperature response of compound animal feeds treated with and ensiled green fodder, hay and grain, containing additives, and incubatcd at 25°C 40 Control IBD:AGS(1:1) IBD:i-butyric acid : 1) mixtures of isobutyraldehyde with other substances, (no additive) 5%. , , ". .2% derivatives of isobutyraldehyde and mixtures of said Day Temp.*C Temp...“C Temp.C derivatives with each other or with other substances. 7 27 24 24 In general moulds and yeasts are the main organisms 14 29.5 26 25 responsible for the deterioration of stored products 2 29 25 24 45 28 - 28.5 25 . 24.5 such as forage, hay, grain and compound animal feeds. 35 27 25.5 24.5 Thus in a screen for possible chemical additives, pre 42 25.5 25 24 liminary experiments were carried out to determine the antifungal and preservative properties of several simple mixture and compounds derived from IBD. The compound feed of Table 2 was tested, containing These preliminary in vitro experiments indicated that 50 various potential preservatives incorporated using mo certain of these compounds, alone or in mixtures inhib lasses as carrier. This material was moistened to ited the development of microbial growth and permit achieve a very high water content (s.50%) and then ted satisfactory storage of forage, hay, grain, com stored in lagged glass jars fitted with thermometers to pound animal feeds, etc. at high moisture contents (e.g. monitor self-heating, and incubated at 25°C for 6 up to 50%). 55 weeks. At the start and end of the experiment the mate The additives listed in Table hereunder showed rial was assayed for various constituents including dry preservative properties when incorporated into com matter (dim), ash, oil, energy, fibre, reducing sugar and pound animal feeds using molasses as carrier for the nitrogen and checked visually for mould growth. additive (see Table 2 for composition of feed). The results obtained are summarised in Table 4. The 60 material treated was of a very high moisture content Table (about 50% m.c.) and stored at a relatively high tem Additives which showed preservative properties in perature, optimal for the growth of many typical stor compound animal feeds - age moulds (i.e. 25°C). Treatment Additive level wiw Therefore it was considered that any additive which 1 BD/Sulphuric acid (40% wiv) 65 resulted in a 30% to 50% reduction in any of the pa mixtures, e.g. 3 vol acid: v BD 2 rameters of Table 4 would be worthy of further consid 2. BDIAGS* (1.1) wiw 5 eration even if they showed signs of visible moulding, 3 BD/formalin (3: viv) 2 provided this was less than in the case of the control. 3,982,028 3. 4 The treatments which emerged as of high potential on age potential the incorporation of water may be limited this basis are as follows: . by the proportion of oil present and is normally in the range 8-10% (w.fw). It would be of considerable advan tage for feed compounders if they could extend the BDiisobutyric acid (3:1) viv IBD/isobutyric acid (l: ) viv range of permissible water contents up to about 18%. BDiisobutyric acid (1:3) wiv At this level spoilage through moulding would be al BDI AGS acid (1: ) viv most inevitable. In addition the use of plastic bags for BDiAcetic acid (3:1) viv the storage of feeds would represent an economic sav BDIFormalin (3:1) w/v. ing over the currently used paper bags. However, even 10 at low moisture contents it has been found that pelleted Table 4 The effect of IBD and derivatives, alone and in admixture, on the storage stahility of approx. 50% m.c. compound feed for six weeks. Application Scif %, losses . rate heating during storage Visible Treatment % (v?w) index DM Energy Moulding Control (c) 56 53 49 -- Control 46 7 72 -- Control f 41 66 57 -- B) 2 64 64 64 - 5 50 59 6 -- BD/IBA (3:1) 2 3 ( : ) . 2 () () () (1:3) 2 () () () IBD/HSO, (25% v/v) 3: 2 6 37 38 ( :) 2 24 37 36 -- 1:3 2 14 13 7 -- BD/AGS ( 1:) 5 3 5 5 BD/Acetic acid (3:1) 2. () 4 l -- BD/Formalin (3:1) . 2 20 () () lsobutanol 2 28 65 54 -- lsobutyl isobutyrate. 2 18 ' ' 54 36 + lsobutanolfsodium, - isobutyrate 2 25' 79 7() -- icates growth, *self-heatinghis index=the growth , sum, , ,of the rise in temperature above ambient due to self-heating on alternate days throughout storage period. In the manufacture of compound feeds the compound feed industry at the present time has to specify thc use of ingredients having a high dry matter, content, i.e. 10-14%. If this range is exceeded there are problems of 40 storage due to the formation of fungal and bacterial species. Thc toxins associated with such microflora feeds "sweat' during storage and cause condensation then limit intakc and animal performance falls off. to build up on thc inner surface of the bag with result In the process of compounding the feed the manufac ing mould growth on the pellets. turer adds steam to the mix prior to pelleting. This has 45 Some of the additives mentioned hereinabove, even the effect of raising the temperature of the mix and though they showed visible moulding in Table 4, were results in gelatinization of the starch, a process which tested with compound feed pellets having the composi results in the formation of stable pellets.